Preparation and use of sericeous solutions



n d St te s.

- 5 sowrrorws V ThomasC WhitnenElizabeth, Jj, i

No Drawing. Application June 25, 1949, i serialiNo. 101,499 L v PREPARATION ANDUsE'oFsEnIeEoUs l This invention relate s to'the preparation of aqueous solutions containing dissolved sericeous material It also includes the application ofsuch solutions for impregnat-fj ing textile fibers with sericeous material; j

In U. S. Patent =2 ,4l7,388,'issued March11;"-1947; I have described a-niethod-for impregnating cellulose fib'ers with sericeousmaterials; The procedurewincludes dis-' y alkali nietal'hyd v being formed in ftheaffiist' step solving silk fibers in an aqueous solution containing an olamine-copper complex and alkali metal "hydroxide is aqueous alcohol, i. e.;' a liquid homogeneous mixture .of

Cellulose fibers are saturated with such" amallowthe:admixture'toistand -untilithe fibers become m ill) dissolves -arid' furnishes a blu to the copper s I one step infthe" aqueous "alcoholicf solution-{ a r 1,111,376 Cc e J??? F515? thealltylolamine is -addedi'slowly to t e mutton." At first a precipitate-ef geo er-ihydroxide'{is fortned, butthis e?solution on continued addi tion of-the alkylolarriin s'lthe ne t st'e' th" quantity of -alkali" rne hydroxide; is" d1 01 aqueous alcohcalic sol tion in alkylblarnineacoppe plexi {UPQI dissolution of this hydroxidedhere alkah kylolamine yand copper salti" 'Theaqueous alcoholie soluti decantationl i 7 v 'lnsteadofi'ss'olving all-of-dh alkali'm 'a'lh y rude Yl' olamine-copper complex; a "p'ortion suffieien 'to react with the alkylolamine"- salt mayi'bei dissolvedi I after separation of 5 the precipitated alkali fnietal salt,

convenient procedu're,asfor"xample by filt' tion r -by.

concentration. i

solved *in {the aqueous alcoholic solution to givefthei it After preparing ='an= aqueous kylolamine-copper complex and alkali; metal hydroxide byuany iof tli'e above-indicated method on can be separated from the precipitated' salf 'bykany dark purple colored massi i The quantity of fibers' I ployediin; this stepmay 'be suificient to soak-Q up all ofthe alcohol and water containing not less than about 60 per cent alcohol by volume, thenthe solution can be employed for treating silk fibers tofurnish a dark purple-colored gummy mass which is soluble in water butvery much less so, and in some instancessubstantially insoluble, in: the aqueous alcoholic solvent. Moreover, the'aqueous solution of this gummy mass can beused foriirnpregnating textile fiberswith sericeous material.

To prepare a solutionof alkylolamine-coppen complex, and alkali metal hydroxide suitable for my purpose, 1 find the following procedure to be .a-convenient one: aGopper pressed to.eliminatetas=much aspossibleiof the' alcoholici aqueous alcoholic solution; or the quantity mayabe 'less" thanithis amount and sonie supernatant liquid. be;present.

,During' mistreatment-ibis fwell Itostiror agitatethe i I mixtu rezoecasionally s35 astoobtain;intiniate' contact 7 between .fibers andliquid. *Afterwardsjdhe supernatant liquid (if any) is; withdrawn and theitreatedjfibers are f liquidiwhichtis held by: them. As the next steppthe 'treated 7: washingto aid in removing the liquid=froiiijthesfibers.:

hydroxide is admixed-with the aqueous 'alcoholic isolyent and to the mixture is added slowlyandin small portions a suflicient'quantity of alkylolamine to dissolve the copper hydroxide in the aqueous alcohol and thereby-furnish a dark-blue colored solution. The r'ate of solution ofcopper hydroxide is very-much slower, in 'rnost'insta'rices, than if water alone were employed 'asthe solvent yConsequently, it'is advantageous to add thealkylolaminein small portions and -to" stir"occasionally the; mixture of copper hydroxide and-aqueousalcoholic solution? of alkylolamine. is effected, then the alkali metal hydroxideis dissolved in the liquid; 'The last-mentioned step maybe accomplished either by addingthe solid. alkali metal hydroxide in any suitable manner. Z v. As a modification of the abovein di cated method; I may use a-copper salt (such as crystallinewcopper chloride) instead of hydroxide; Such-a salt should exhibit anap- After solution of the copper compound material containsv copper cbmpp nds, and; :may :contain to the solution ofcopper-complex and stirrin g gor by ad.- I mixing an aqueous solution of the alkali metal hydroxide with the aqueous'alcoholic solution; shouldanytlheat develop during dissolution rofi the"alkali metalrhydroxide in the aqueous alcohol, it is'desirab1e.toacoolithe latter pre'ciable orv substantial solubility inv the alcohol o'rtin the aqueous alcohol; After the copper 's'alt is dissolved;then

.fibers are washed one ormore times with" portions of Lthe, I

aqueous alcohol; 7 and s the fibers :are% pressed afteri each Thetreated and washed dark colore'd mass obtaine in this manner then 'is iextracted with wat'er; -Extraction:can

. be I effected :iIfl: anyt -convenient: manner,- i .as fo'r: example, admixing the :inass awith;water,allowingaithewrnixture to stand =forj a' suitabl e length zof time,:- .and. ,tozseparate the aqueous .-liquid; frorii .any ;unfdissolved; Ina-L terial. a Thei cleaiflxrpurplefcolored, Laqueousliquids i'ob} f tain'edfas, the filtrate, since it-;cor 1 tains dissolved sericeous with sericeous material. :2 J i 1 lIo leiTect such; impregnation, the; textile ,fibersv are I saturated.-'(injany,:suitable;oraconvenient manner y-witti thisvaqueolis'-so1utiona: Afterwards," the-Lliquid-saturated .f

fiber'slare washedewith dilute aqueousv :acidf then with;

water, f; and Efinally a are L dried; Or; the saturate "fibers may bedried (e. g;, by :exp osure'to the atmosphere),

tthen; washed (successively with frdilute aqueous aci' water, and 'dried. t\.-As .the-aqueous solution: :of: se'ri s'alts.,;with the; opper 1 compounds and with, 1 the alkali stances are hydrochloric, acid, ,sulfuric ,acidza'nd acetic a i -1. l ough 'm snof the oppe .a aa lif e al salts will be eliminatedgfrom .theziibers during t he;,acid

wash, nevertheless; thefibers ,should be washed. afterwards with. water so as to obtain substantially complete elimination of all salt's a id-acidt r 1S; necessary; to; use p n,

The following examples will illustrate my invention.

Example 1.A solution of copper complex in isopropyl alcohol was prepared in the following manner and by using the following proportions of materials: 6 parts of isopropyl alcohol (99 per cent) were admixed with 4 parts of water. To the resulting homogeneous liquid was added 0.24 part of solid sodium hydroxide. As the latter dissolved, the liquid separated into two layers. After solution of the alkali was complete, parts of diethanolamine were added to the liquid mixture and, on stirring, a homogeneous alcoholic solution of the alkylolamine and alkali metal hydroxide was obtained. Next, 0.1 part of copper hydroxide was added, and the mixture of solution and solid hydroxide was allowed to stand (with occasional stirring) until all of the copper compound dissolved and the solution was deep blue in color.

Silk fibers were admixed with the alkaline solution of diethanolamine-copper complex and worked therein until they became dark purple or almost black in color.

Afterwards, the fibers were separated from the solution and washed with some of the aqueous isopropyl alcohol which was employed as a solvent. Next, the treated fibers were admixed with a sufficient volume of water so that, on stirring, nearly all of them dissolved in the aqueous liquid. The latter was filtered to eliminate a small quantity of undissolved material.

Unbleached cotton cloth was saturated with some of this aqueous solution and then dried by exposure to the atmosphere. The cloth then was washed succes sively with dilute aqueous hydrochloric acid and water and again dried. This sample of fabric had a smoother and fuller feel than the untreated fabric.

Example 2.A solution of alkylolamine-copper complex was prepared by admixing the following substances in the proportions indicated: parts of aqueous ethyl alcohol (70 per cent), 3 parts of ztriethanolamine and 0.2 part of copper hydroxide. After the copper compound had dissolved, 0.3 part of sodium hydroxide was dissolved in the dark blue alcoholic solution. The dark blue liquid then was admixed with silk fibers and the mixture allowed to stand at room temperature for 40 minutes, stirring the mixture occasionally. The fibers became very dark in color and almost sticky or gummy. The alcoholic liquid was separated from ithe fibers, the latter were washed twice with 70 per cent ethyl alcohol, with pressing of the .fibers after each wash to eliminate .as :much alcoholic liquid as possible, and then the washed fibers were admixed with about times their weight of water, and this step resulted in solution of a large proportion of the treated and -washed silk. The aqueous liquid was separated from undisso'lyed material by filtration.

Bleached cotton cloth was saturated with this aqueous solution, then allowed to drain and to dry while -exis :posed to the atmosphere, and afterwards the fabric was washed successively .with dilute aqueous sulfuric acid and water, and dried. This fabric again was impregnated with the aqueous solution of sericeous material, ithen 'washed successively with dilute aqueous .acid and water, and dried.

A portion of the treated bleached cotton cloth and tone of the untreated bleach fabric were dyed separately. In each instance, 100 parts of water and 5 per cent (on weight of sample) of a red acid dye were used. The dye baths were warmed -'to -C., the samples entered, and the baths kept at a temperature of 40 to C. for a period of 2 hours. The baths then were allowed to cool to room temperature, the samples re moved and rinsed well with cold water, and dried. 'The untreated fabric was a light pink in color while the treated cloth was a full red in color.

Example 3.One part of copper "chloride was dissolved in 15 parts of per cent aqueous ethyl alcohol and to the solution was added Z-methyl-Z-aminopropanediol-l,3 until a blue colored liquid was obtained and all the copper compounds were dissolved. Next, sufiicient potassium hydroxide was dissolved in the bluecolored liquid to .efiect substantially complete precipitation of the chlorine as potassium chloride. The latter was separated from the solution of alkylolamine-copper complex by filtration. Afterwards, there was dissolved in the filtrate sulficient potassium hydroxide to furnish substantially a 2 per cent solution of the alkali metal hydroxide. I a

To the resulting solution, which contained both copper complex and alkali metal hydroxide, were added silk fibers, and these were permitted to remain in contact with the solution at room temperature for 1 hour. Afterwards, the alcoholic liquid was separated as well as possible from the treated mass of fibers, the latter were washed with two successive portions of the 70 .per cent aqueous alcohol with separation of the wash liquid each time as well as possible, and then the mass of fibers was admixed with 30 times its weight of water and the admixture allowed to remain overnight at room temperature. The aqueous liquid next was separated from undissolved material by filtration. Titration of the filtrate (with standardized aqueous acid) indicated its total alkaline content was 0.08 per cent (calculated as potassium hydroxide) Unbleached cotton cloth was saturated with some of this aqueous solution of sericeous material and then dried at room temperature. Afterwards, the fabric was washed successively with dilute aqueous sulfuric acid and water, and dried. This treated cloth possessed a smoother and fuller feel than the original untreated fabric.

Aportion of this treated cloth and one of the untreated fabric were dyed separately, using :in each instance 70 parts of water per 1 part of sample and 5 per cent (on weight of cloth) of a red acid dye. The samples were placed in the respective baths at room temperature, the) temperature of the baths then increased to 40 C. and kept at 40 to 45 C. for 1 hour. permitted to cool to room temperature, the samples removed and rinsed well with tap water, and dried. The untreated cloth was a very light pink in color while the .treated sample was a light red.

Example 4.--To cc. of 70 per cent aqueous .ethyl .alcohol was added 1 g. of copper hydroxide and to the mixture was added ethanolamine slowly until the copper compound dissolved. The resulting blue solution was diluted with the alcohol until the total volume was cc. :Suliicient solid sodium hydroxide was dissolved in the so lution to give substantially l :per cent concentration of ithis alkali. All of this solution was admixed with silk fibers and the mixture allowed to stand at room temperature with occasional stirring) until the fibers had changed in appearance to a dark-colored gummy mass. The latter then was separated from :the alcoholic solution as well as possible by pressing, and afterwards washed well with two successive portions of 70 per cent aqueous alcohol.

The treated and washed fibers (after being freed as much .as possible from the aqueous ethyl alcohol by pressing) were admixed with 100 cc. of water .and the'mixture allowed to stand for three days at room temperature.

' Next, the aqueous liquid and undissolved material were :separated :by filtration. .In this instance, the filtrate or aqueous solution of sericeous material had a total al- 'ltaline content (as estimated by titration of a portion of it with standardized aqueous acid) of 0.46wper cent, calculated as sodium hydroxide.

Unbleached cotton yarn was saturated with lthlS aqueous solution by immersion in some of it for 20 minutes at room temperature. Afterwards, the yarn was allowed ito drain .and then' was washed successively :with dilute aqueous sulfuric acid and-water, :and idriediat 27.0 (to 759 The baths then were.

.5 C. This sample of treated yarn .and one Qfjthe I Intreated yarn were dyed separately by. .imm ersion., overnight (about 16] hours) in' an aqueous solutionqconsisting of 100 parts of water per lpart of nand per cent (on. weight of yam of a' b1u e su ntiyedye. Next, the samples were removed 'fr'om therespectiyje baths, rinsed with cold wa't'er, and driedQ..flhe'tre ed sample of yarn wasdy ed to J a, darker color the untreated one.. 1' '1 Example Sr-A solution consisting fof' S O propyl alcohol'(9 9lper Q V admixed with 0.7 g., I Y i ture trieth'anolamine' was; added. copper compound" dissolved}. a was diluted to a volume off' 96'fc alcohol and afterwardsfadmixed with an tion consisting of 2"gflof potassiu'm,hydroxide m 4 c. i

of water. These steps furnished a "darkiblu aqueo us alcoholic" solution of alkylolamine coppier complex and alkali metal hydroxide.

A suflicient volume o'f thissolution" 7 I 8 g. of silk fibers so that the fibers r'e ;tho ughl'y moistened but there was no L excess'liquid jA fte proximately minutes, the wet fibers wer'e' pres the aqueous alcoholic liquidlseparating thereupon substantially colorless but strongly alkalinej fter eliminating as much alcohol as possible fro'rnj' th fibers, the latter were moistened again with'somepfthe. l alcoholic copper solution arid'allowed temperature until substantially 'colorles sander more ut strongly .fibers 13.5, g. and m i s? P room'teinperature Ifor3.f5f hours. The supernatant liq.-

uid' was 'poured otf and asjmuch liquid expelled from e 'ng 3 8; percen it calculate The samples :vlferei immersed infthe respective .baths;for 5 urs atroom t emperature; then 'remoyed frih'sedlwell' alkaline aqueous alcoholic liquid was separated there from on pressing. This series off'operaltions was re} peated untilall of the blue-colored,alcohglicfi luf il had been used in"treatingfthe"si llc ffib'ers'; Tli which had become a very dark colored mass cc. each time and alsopressing the mass of fi to eliminate as much aqueous alcohol "w possible. Thermassof fibers then wa twice with 86 per cent aq'ueou's isoprop yl alcoholgusirig H rxed wit 0 cc. of water and, after the mixture had stood l) I minutes, the aqueous solution 'wass dissolved material by filtratio s estimated (by titrationof a" tion withstandard aqueous acid) thatythe alkal' the aqueous extract 'w .25' Y potassium hydroxide.

Bleacht cotton 'y arn the aqueous extract by utes at room temperature posure to the atmosphe with dilute aqueous sulf u and dried at a temperatur Y 'Wre d d s ifi a lvru'sm c fla consisting of 100 parts of water per; 1 p

per cent(onweightofsample) offla baisrcmed samples were immersed [in the respective b temperature, then the temperature of the creased to C over a periodof one,- kept at 60 to .C. tor thir ty minutes the baths. were allowed to coolto room mperature;

the samples were removed and. rinsed. with cold water,

y ;d ctl' 1 4a d ker. Qq qr and dried. The treate than the untreated sample;

Example tha am. n 1 a iiad e i s e t rt mixture o 0 f W 'an lsqfacopper. hy o id until all of the copper compound dissolved. The yolume of the solution increased to 4 0 cc. Ihen .100 stantially anhydrous tertiary .butyl alcohol lwere with the blue. aqueous solution. of. allgyl complex andthe mixturewas stirred: liquid was b a latheiquid was .1$.Q s r ficient potassium hydroxide to give substantially; per cent solution ofthe alkali metalhydroxide, The aqueous alcoholic solutio'ri was adrn xed with I r A te wa d portion of the aqueous olu;

- c eous ri'le tte r ial as pr pal'ed, Example line 1 oomternperature.

ixturepermitted to ,standat hifibets s possible; T el fihaniwe e washed We l. with several portionsjoff dq bt ls tcr, -bi1tyl alcohol (made by mixing. alcoholand wat'er "in; the proportion. by volu of'IOQZ loiithe former to"40 of;th e latter) After as much, as .possible of the aqueousalcohol ersyflthe latter Wereladmixed with IOOfcc.v of M t of thetre ed fibers dissolved in' the aqueous n i di' ol T v1 t t nf Ofjthe fi te ed, lidard fqueofisl. acidindicated ah d 5 rsj v wit ute. aqu usqac'idf w te nd1 rj d. to C; This treated) soasa l p' un r a e arnw r ed {to drainwa nd 10', dry hi e washed successively with dilute aqueous sulfufi? ac d and with water and again dried by exposure to the atmosphere. This treated fabric had a smoother feel and somewhat more body than the untreated cloth and also possessed that property which is described as scroop.

Example 9.-To a solution consisting of 2 g. of crystalline copper chloride (CuClzQHzO) in 20 cc. of water were added '80 cc. of normal propyl alcohol. Then to the resulting clear homogeneous liquid ethanolam'ine was added slowly until a clear blue solution of the alkylolamine-copper complex was obtained. In this liquid was dissolved sufficient potassium hydroxide to react with the copper chloride, and afterwards the precipitated potassium chloride was separated by filtration; Next, sufficient potassium hydroxide was dissolved'in the filtrate to give substantially 3 per cent of the alkali metal hydroxide in solution.

The solution of alkylolamine-copper complex and alkali metal hydroxide was admixed with approximately 15 g. of silk fibers and the mixture permitted to stand (with occasional shaking) at room temperature for 30 minutes. Afterwards, the substantially colorless aqueous alcoholic liquid was separated from the treated silk fibers and the latter were washed four successive times with 80 per cent aqueous n-propyl alcohol (using 100 cc. of the alcoholic liquid each time).

After separating the alcoholic liquid as well as possible from the treated fibers each time by filtration, the fibers then were admixed with 100 cc. of water and the mixture allowed to stand for 1 hour at room temperature; The aqueous liquid was separated by filtration from the fibers and the latter extracted a second time in the same manner with another 100 cc. portion of water.

Bleached cotton cloth was saturated with some of the second aqueous extract, and then was allowed to drain and to dry by exposure to the atmosphere. Next, the substantially dry impregnated fabric was washed with dilute aqueous sulfuric acid containing 5 per cent of dissolved sodium sulfate, and afterwards washed with water, and air-dried.

This treated fabric and also a portion of the original untreated fabric were dyed separately. In each instance the dye bath consisted of 100 parts of water per 1 part of cloth and per cent (on weight of sample) of a substantive dye (Primuline). remain in their respective baths overnight at room temperature, then were removed, rinsed well with water'and dried. The treated cloth was darker in color than the untreated fabric and also possessed a smoother feel.

Example 10.Diethanolamine was added slowly and with stirring to a mixture consisting of 2 g. of copper hydroxide and cc. of water until all the copper compound dissolved and a clear blue solution was obtained; This liquid then was diluted with 80 cc. of normal propyl alcohol. Afterwards, sufficient potassium hydroxide was dissolved in the aqueous alcoholic solution to give substantially 4 per cent of the alkali metal hydroxide. Titration of a portion of this solution with standard aqueous sulfuric acid indicated its total alkalinity to be equivalent to 11.08 g. of potassium hydroxide per 100' cc.

Eight grams of silk fibers were admixed with 80 cc. of this aqueous alcoholic solution and the mixture allowed to stand (with occasional stirring) at room temperature for 30 minutes. The alcoholic liquid, which had only a tinge of blue color, was separated as completely as possible and the dark colored residue (of treated silk fibers) was washed 4 successive times with 80 per cent aqueous n-propyl alcohol. In each instance, the volume of alcoholic liquid was 80 cc., the treated fibers were worked therein for 10 minutes at room temperature, and the liquid was separated from the insoluble mass by filtration.

After the treated fibers were washed with aqueous alcohol they were extracted twice with water. Each time a volume of 80 cc. of water was employed, the fibers re- The samples were allowed to I;

its

at t

8 mained in contact with the aqueous liquid for 10 minutes at room temperature, and then the aqueous liquid was separated by'filtration. The total alkalinity of the first aqueous extract was ascertained to be equivalent to 1.91

g. of potassium hydroxide per cc. and that of the second extract to be equivalent to 0.76 g. of potassium hydroxide per 100 cc.

Example 11.Unbleached cotton cloth was saturated with the first aqueous extract of Example 1.0 by immer sion therein at room temperature. Afterwards, the impregnated cloth was dried by exposure to the atmosphere. When dry, it was washed with dilute aqueous sulfuric acid containing 5 per cent of sodium chloride. Next, it was washed with water and dried.

' This sample of treated cloth and one of the untreated original fabric were dyed separately. In each instance a dye bath consisting of 100 parts of water per 1 of cloth and 5 per cent (on weight of sample) of an acid dye (Fast Red SS Extra) was used. The samples were kept immersed in the respective baths for 3 hours at room temperature, then removed, rinsed well with water and dried. The untreated fabric was a light pink in color while the treated cloth was a good full red in color. ter cloth possessed a smoother feel and more body.

Example 1'2.-Unbleached cotton cloth was saturated with the second aqueous extract of Example 10 by immersion therein at room temperature. Afterwards, the

impregnated cloth'was dried by exposure to the atmosphere. When dry, it was washed with dilute aqueous sulfuric acid containing 10 per cent of magnesium sulfate (MgSO4-7HzO). Next, it was washed with water and dried.

This sample of treated cloth and one of the untreated original'fabric were dyed separately. In each instance a dye bath consisting of lOO parts of water per 1 part Of cloth and 5 per cent (on weight of sample) of a basic dye (Safranine'Y Ex. Cone.) was used. The samples were allowed to remain immersed in the respective baths overnight at room temperature, then removed, rinsed well with'water, and dried. In this case, the two samples were not dyed to shade of color, as the untreated fabric was a rusty, brownish red whilethe treated cloth was a bright, clear red.

Copper hydroxide employed in the above examples was prepared in the following manner:' A copper salt, such as copper sulfate (CuSOr-fiHzO) or copper chloride (CuClz-ZHQO); was dissolved in water and then about one-fourth its weight of ammonium sulfate or ammonium chloride was dissolved in the solution.

ity of the aqueous extract is always less than the alkalin ity of the aqueous alcoholic solution of alkylolamine copper complex and alkali'metal hydroxide used for the treatment of silk fibers. This condition is due to separating the aqueous alcoholic treating liquid from the fibers and washing them with aqueous alcohol before they are extracted with water. Washing with aqueous alcohol effects not only removal of alkali metal hydroxide from i the mass of treated silk fibers but also removal of any excess alkylolamine which may have been employed when the copper compound initially was changed into the alkylolainine-copper complex and in addition removal of any alkylolaminc-copper complex which may not be in combination with sericeous material. The degree or extent to which the alkaline bodies (alkylolamine, alkali' metal hydroxide and any uncorn'bined alkylolaminecopper complex) are eliminated will depend ofcourse upon the number ofwas'hings with aqueous alcohol given Also, the lat- I An aqueous solution'of sodium hydroxide was slowly admixed with the so- The copper hythe treated silk fiber'sprior to extractionof the watera t a. v

Washing the treated fibers; asmentroned above, and their extracting them with waterv furnishes an aqueous ex act which has a very small ,proportiornless Qjfper cent,

of alkali metal hydroxide'. If fs'uch tr atedffibers be washed several .times with 'aqueous alc'oholpriorto tracting with water, then the aqueousextractwill" con am the alkylolamine (in the form of alkylolam' p er; complex combined with sericeous lmaterial) j asfsubstam tially the only alkali'dissolved in the aqueousliquidl,

As shown in Example], an aqueou according to this invention can be use terial prepared as des'cribedginU. S

of wool fibers. If anfaqu eous solution of-seri ous' m stituted therefor, then th e" arme s be colrnegray black in color and this color is notfelimm ed 911 washing the wool fibers withaque ou's' acid. fDi scoloring'ofiwool can be effected with anjaqueous'solution alkylola rmnecopper complex and alkalie rnetal hYdlfQXltlQlIl hi chthe proportion of'the latter compound falls with disclosed in U. S. 2,417,388. These res dicate that alkali metal hydroxidecopper complex (either as such or w enpresentflwith sericeous material) react with wool'fiber o give' copp er sulfide as a reaction product. 1 On thefot he fhand, since the aqueous solutions (or extractsflprepare to this invention contain'such a smallpr opo o solved alkali metal hydroxide, or are substa thereof, they are applicable notonlytfor th U vegetable fibers (such as "cotton and linen) also the treatment of animal fibers (such as 'waer'and silk) without reacting with them in an undesirable manner.

From the foregoing disclosures it will be s een that my invention includes a method for preparing an aqueous solution of sericeous material suitable for the treatment of variousfibers. This method comprisesvtreating silk fibers with an aqueous alcoholic solution ofuan alkylolaminecopper complex and an alkalimetal hydroxide; then-separating the treated silk fibers as well as holic solvent, and afterwardsextracting the treated and washed fibers with water. 7

My invention also includes impregnating textile fibers 4 i with the aqueous solution of sericeous material (which is prepared as just indicated) and then washing the impregnated fibers with an aqueous solution of an acidic agent and subsequently with water. As an alternative possible frornthe alcoholic solution, washing them'witlizthe aqueous aldoprocedure, the fibers impregnated with the aqueous solu-- tion of sericeousmaterial canbe dried at substantially atmospheric orroom temperature, then washed with the aqueous solution of acidic agent andfsubsequentlyfwith water.

As mentioned above, an aqueous alcoholicf SOIVGnbgiS.

used as the liquid medium in which are dissolved the alkylolamine-copper complex and the alkali metal hydrox ide and also as the liquid with which the treated silk fibers are washed. By the term of aqueous alcoholic solvent I mean a mixture of water and alcohol in which the latter is present in the greater'proportion by volume.

The alcohols which I prefer are saturated acyclic compounds, such as ethyl, isopropyl or tertiary butyl alcohol, and possess boiling points at atmospheric pressure which do not exceed about 120 C. ,The alcohols suitable for my purpose can be primary, secondary or tertiary compounds and should dissolve suflicient water or be sufii-" ciently soluble in water so that an aqueous alcoholic:

solvent containing at least about 60 per cent by volume of the alcohol can be prepared. It should be understood that this proportion represents the lower limit of alcohol in 10 45 volumes of substantially, anhydrous isopropyl alcohol, an'dilovolum es of water. ,The alkylolarnines'employed by me for lmak'in githe cdppercorriplexe lustrated, by monoethanolamine (9! hea am tha l mi iand. fi a s am n either nohydroxy or -polyhy droxy e alk may -beeitherja m pt iott caper complexserlc H "ater1a1, a yery s aILrr PPUiQ 9 lk li met ydr. washedwithanfaqueous sol tio ofan acidic alg dried at substa ing' step in coagulating andlorv flocculatin'gjthe seticeous material held'by the impregnatedfibers. j Some care'must.

be exercisedin'selection of the salt, asone whichreacts with the acidicf agent to furnish an'insoluble'productis 'undesirableI For example',1barium chloride is not a suitable salt withtan aqueous solution of sulfuric acid. However, bariumchloride may be used with-an aqueous'soluf v tion of eitherhydrochloric acid or acetic acid. The pro-.

portion ofsaltdissolvedin the aqueous solution of acidic agent may be varied within wide limits, as for example, 5 10Jor 15. per cent. For the purposes of this invention,

- I. include ammoniumsalts with the alkali'metalsalts;

After they have been Washed with. the aqueousacidic agent, the fibers should be washed sufliciently 'well with water so that elimination of substantially all salts and acidic'agent therefrom is eifected.

What I'claimis:

. V 1-. The process which comprises treafting silk fibers with an alkylolamine-c opper .complexj'and an alkali metal ,hy -.t droxide dissolved in fan" aqueous alcoholic solvent, the j proportion of saidalkali metal hydroxide being not more thanabout 4 percent and nottless than about O.5 per the solvent and that solvents possessing a greater proportion, say 70, or percent can be used. Moreover,

the aqueous alcoholic solvent may contain a inixtureof two or more alcohols, as for example a solvent consistlng of 45 volumes of substantially anhydrous ethyl alcohol,

centtheweight of said solution, and the aqueous alcoholic solvent cons'isting substantially of only'water and a .sat-

urated acyclic alcohol. of :at'; least two carbon atoms whose boiling point; is nOLg'reat er than about (land containing at least about: 60 per cent by volume. of said alcohol, separating the aqueous alcoholic} solution from said fibersfwashing the treated fibers with th.aqll6G1lS;, alcoholic solvent, and extracting said treated and washed fibers with water;

agent oftentimes aids during the wash;

2. The process according to claim 1 in which the alkali metal hydroxide is sodium hydroxide.

3. The process according to claim 1 in which the alkali metal hydroxide is potassium hydroxide.

4. The process which comprises treating silk fibers with a monohydroxy alkylolamine-copper complex and an alkali metal hydroxide dissolved in an aqueous alcoholic solvent, the proportion of said alkali metal hydroxide being not more than about 4 per cent and not less than about 0.5 per cent the weight of said solution, and the aqueous alcoholic solvent consisting substantially of only water and a saturated acyclic alcohol of at least two carbon atoms whose boiling point is not greater than about 120 C. and containing at least about 60 per cent by vol ume of said alcohol, separating the aqueous alcoholic solution from said fibers, washing the treated fibers with the aqueous alcoholic solvent, and extracting said treated and washed fibers with water.

5. The process according to claim 4 in which the monohydroxy alkylolamine is ethanolamine.

6. The process according to claim 4 in which the monohydroxy alkylolamine is isopropanolaminc.

7. The process which comprises treating silk fibers with a polyhydroxy alkylolamine-copper complex and an alkali metal hydroxide dissolved in an aqueous alcoholic solvent,

the proportion of said alkali metal hydroxide being not more than about 4 per cent and not less than about 0.5 per cent the weight of said solution, and the aqueous alcoholic solvent consisting substantially of only water and a saturated acylic alcohol of at least two carbon atoms whose boiling point is not greater than about 120 C. and containing at least about 60 per cent by volume ,of said alcohol, separating said aqueous alcoholic solution from said fibers, washing the treated fibers with the aqueous alcoholic solvent, and extracting said treated and washed fibers with water.

8. The process according to claim 7 in which the polyhydroxy alkylolamine is diethanolamine.

9. The process according to claim 7 in which the polyhydroxy alkylolamine is triethanolamine.

10. The process which comprises treating silk fibers with an alkylolamine-copper complex and an alkali metal solvent consisting substantially of only water and a saturated acyclic alcohol of at least two carbon atoms whose boiling point is not greater than about 120 C. and containing at least about 60 per cent by volume of said alcohol, separating the aqueous alcoholic solution from said fibers, washing the treated fibers with the aqueous alcoholic solvent, extracting said treated and washed fibers with water to form a water extract containing an alkylolamine-copper complex and an alkali metal hydroxide and dissolved silk, the proportion of said alkali metal hydroxide being less than about 0.5 ,per cent the weight of said solution, impregnating textile fibers with said Water extr t, ash n a pr gnat d fi e s h an u u olut n somet a a d a en f rm watevsoluble lt thsai al l lamine-cpppe c mp ex a d h a alkali m a h d oxid and a t r ar w i s tile fibers with water.

11. The method as in claim 10 in which the textile fibers are wool fibers.

12,. The method as in claim 10 in which the textile fi r a e si k fibe s- 13. The method as in claim 10 in which the alkylol amine-copper complex is a monohydroxyalkylolaminer soa s; omplex- 14. The method as in claim 10 in which the alkylolamine-copper complex is a polyhydroxyalkylolaminecq p r w p s References Cited in the tile of this patent UNITED STATES PATENTS 

10. THE PROCESS WHICH COMPRISES TREATING SILK FIBERS WITH AN ALKYLOLAMINE-COPPER COMPLEX AND AN SILK METAL HYDROXIDE DISSOLVED IN AN AQUEOUS ALCOHOLIC SOLVENT, THE PROPORTION OF SAID ALKALI METAL HYDROXIDE BEING NOT MORE THAN ABOUT 4 PER CENT AND NOT LESS THAN ABOUT 0.5 PER CENT THE WEIGHT OF SAID SOLUTION, AND THE AQUEOUS ALCHOLIC SOLVENT CONSISTING SUBSTANTIALLY OF ONLY WATER AND A SATURATED ACYCLIC ALCOHOL OF AT LEAST TWO CARBON ATOMS WHOSE BOILING POINT IS NOT GREATER THAN ABOUT 120*C. AND CONTAINING AT LEAST ABOUT 60 PER CENT BY VOLUME OF SAID ALCOHOL, SEPARATING THE AQUEOUS ALCHOLIC SOLUTION FROM SAID FIBERS, WASHING THE TREATED FIBERS WITH THE AQUEOUS ALCOHOLIC SOLVENT, EXTRACTING SAID TREATED AND WASHED FIBERS WITH WATER TO FORM A WATER EXTRACT CONTAINING AN ALKYLOLAMINE-COPPER COMPLEX AND AN ALIALI METAL HYDROXIDE AND DISSOLVED SILK, THE PROPORTION OF SAID ALKALI METAL HYDROXIDE BEING LESS THAN ABOUT 0.5 PER CENT THE WEIGHT OF SAID SOLUTION, IMPREGNATING TEXTILES FIBERS WITH SAID WATER EXTRACT, WASHING SAID IMPREGNATED FIBERS WITH AN AQUEOUS SOLUTION CONTAINING AN ACIDIC AS FORMING WATER-SOLUBLE SALTS WITH SAID ALKYLOAMINE-COOPER COMPLEX AND WITH SAID ALKALI METAL HYDROXIDE, AND AFTERWARDS WASHING SAID TEXTILE FIBERS WITH WATER. 